DE2922374A1 - METHOD FOR THE PRODUCTION OF BENZOXANTHENE AND BENZOTHIOXANTHENE DYES - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 79 / F 134

Dr. KL / La

Process for the preparation of benzoxanthene and benzothioxanthene dyes

From DE-PS 20 25 291 it is known, isomer mixtures of the benzoxanthene or benzothioxanthene materials general formulas

and

Yes

Ib

wherein X is an oxygen or sulfur atom, R is an optionally substituted alkyl radical, acyl radical or benzilsulfonyl radical, R ₁ and R_ are hydrogen or halogen atoms, alkyl, phenyl, acyl / acyloxy, carbalkoxy, alkoxy, nitro, alkylthio or Alkylsulfonyl groups or together a fused benzene ring, R ₃ and R hydrogen or halogen atoms, phenyl groups, alkyl, alkoxy, carbalkoxy groups with 1 to 4 carbon atoms or nitrile groups, R ^ and R, hydrogen atoms or optionally substituted alkoxy groups with 1 to 4 C atoms mean to be prepared by adding benzoxanthene or benzothioxanthene-3,4-dicarboxylic anhydrides of the general formula

030051/0039

or the derivatives of the general formula

lt .. _t COOR ₇

COOR,

III

in which X, R ₃ , R ₄ , R ₅ and R _{ß have} the meanings given above and R_ denotes a hydrogen atom or an alkyl group, with a compound of the formula

/ J-CHCOOR ₇

IV

and or ._

CH

CO

wherein R ₁ , R ₀ and R- have the meanings given above and R "denotes a hydrogen atom or a hydroxyl group, ^{heated in the presence of alkali to temperatures between about 150 °} C. and about 260 ^° C. and the compounds thus obtained, consisting of the Mixture of isomers of the general formulas

and

Via

VIb

OBIGiNAL INSPECTED

in which X, R ₁ , R _37, R ₃ , R ₄ , R ₅ and R _{g have} the meanings given above, alkylated or acylated.

The condensation of the compounds II or III with the compounds of the formula IV or V takes place in the majority of the examples in the melt, but can also take place in a polar solvent, such as N-methylpyrrolidone. The intermediate product thus obtained, the mixture of isomers of the formulas VIa and VIb ₇ , is isolated in each case before it is fed to the subsequent alkylation or acylation reaction. However, these intermediate products show an extremely poor filtration behavior, so that this isolation step requires a considerable amount of time and equipment.

It has now been found that the compounds of the formula Ia and Ib can be produced in a particularly advantageous manner if the condensation and alkylation or Acylation reaction without isolation of the intermediates performs. It is surprising that this considerable process simplification does not result in a deteriorated yield or purity of the end product must be bought.

The invention thus provides a process for the preparation of the above-characterized isomer mixtures of compounds of the general formula Ia and Ib by heating compounds of the formula II or III with compounds of the formula IV and / or V in the presence of alkali to temperatures between about 150 and about 260 ⁰ C, and then alkylating or acylating the mixture of isomers of formulas vIa and VIb, characterized in that one carries out the reaction in a highly polar organic solvent without isolation of the isomer mixture of the formulas vIa and VIb.

Those in DE-PS 20 25 are used as strongly polar solvents

030051/0039

named solvent, preferably N-methylpyrrolidone, in Consideration. Of course, the solvent must be stable at the reaction temperatures and against the reactants be inert, i.e. not alkylating or acylating and not be alkylatable or acylatable »

The alkali required for the condensation can be an alkali hydroxide carbonate or acetate, which are preferred Potassium acetate and potassium carbonate.

Particularly preferred are the condensation reaction is carried out in the presence of potassium acetate or potassium carbonate in N-methylpyrrolidone at a temperature of 200-210 ⁰ C. The reaction solution obtained can then be reacted directly with the alkylating or AcyIierungsmittel.

If the condensation is carried out in the presence of alkali acetate, then it is advisable to use the one that is released To separate acetic acid, if an alkylation reaction with alkylating agents is intended, which with this Acetic acid can react, for example dialkyl sulfates. Otherwise, not only is an increased use of alkylating agents required, but the resulting ethyl acetate can also be used as a precipitant for the intermediate product Formulas VIa and VIb are used.

The alkylation and acylation are carried out in the manner known for phenolic compounds. Suitable alkylating agents are especially the dialkyl sulfates, especially lower ones Dialkyl sulfates such as dimethyl sulfate or diethyl sulfate, Alkyl halides such as methyl chloride or benzyl chloride, alkylene oxides such as ethylene oxide or propylene oxide and aryl sulfonic acid esters such as methyl p-toluenesulfonate. as Acylating agents are aliphatic or aromatic carboxylic or sulfonic acid chlorides or carboxylic acid anhydrides, such as acetyl chloride, propionyl chloride, benzoyl chloride, benzene

030051/0039

sulfonic acid chloride or acetic anhydride into consideration.

To isolate the end product from the reaction solution, it is expediently cooled and a precipitant is added. Suitable such precipitants are organic liquids which are miscible with the reaction medium, in which the dye is sparingly soluble and which can be easily separated from the reaction medium. Lower alkanols, in particular methanol, are suitable.
10

The dyes are obtained in high yield and with the high purity required for fluorescent dyes.

The invention is explained in more detail in the following examples. Percentages relate to weight.

example 1

In a stirred tank reactor a mixture of 400 kg of N-methylpyrrolidone, 104.6 kg phenylacetic acid and 62.8 kg of potassium acetate is heated to 8O ⁰ C. 196 kg of benzothioxanthene-3,4-dicarboxylic acid anhydride are then added and the mixture is ^{heated to 180 °} C. over the course of 2 hours. After stirring for 1 hour at 180 ⁰ C the reaction temperature to 200 - increased 210 ⁰ C and stirred for 8-10 hours at this temperature.

After the reaction has ended, 63 kg of 50% strength sulfuric acid are run ^{in at 200 ° C. over the course of 30 minutes.} The reaction mixture is cooled to 120 ⁰ C, at about 120 130 ⁰ C and about 65 to 95mbar (5 0 - 70 Torr) of acetic acid and water up to a head temperature of 13O ⁰ C at 80 mbar (6 0 Torr).
35

When the distillation is over, 300 kg of N-methyl

030051/0039

pyrrolidone was added and 68.2 kg of potassium carbonate were added. The reaction mixture is stirred for 30 minutes at 12O ⁰ C and then cooled to 80 to 85 ⁰ C. A further 14 kg of potassium carbonate are added and ^{methylated at 80 to 85 °} C. with 160 kg of dimethyl sulfate within 1-2 hours. When the reaction has ended, the mixture is subsequently stirred at 80-85 ^° C. for _{2 hours;} the product is then with 400 kg of methanol at 30 - like 4O ⁰ C and at 15 ° C isolated on a pressure filter. A bluish-tinged red, strongly fluorescent dye / consisting of an isomer mixture of the formulas is obtained in good yield

QCH.

and

Example 2

In a stirred tank to be 76 kg benzothioxanthene-3,4-dicarboxylic anhydride, 37.5 kg Phenylacetic 25 kg of potassium acetate and 200 kg of N-Methyl-pyrrolidone at 180 ⁰ C heated. After stirring for 1 hour at 180 ⁰ C is heated to 200 ⁰ C and stirred for 6 hours at this temperature.

When the reaction has ended, the mixture is ^{cooled to 110 °} C., 75 kg of acetic anhydride are added dropwise over the course of 20 minutes and ^{the mixture is stirred at 110 °} C. for 2 hours. The mixture is then ^{cooled to 20 °} C., 200 1 × methanol is added, the mixture is stirred for 1 hour and the product is isolated on a pressure filter. In good yield, a pure, bluish «-red fluorescent-

030051/0039

the dye obtained, consisting of a mixture of isomers of the formulas

OCOCH ₃ and

COCH.

Example 3

79.5 kg of 10-methoxy-benzoxanthene-3,4-dicarboxylic acid anhydride, 37.5 kg of phenylacetic acid, 25 kg of potassium acetate and 200 kg of N-methylpyrrolidone are placed in a stirred kettle. ^{The reaction mixture is heated to 180 °} C. in the course of 2 hours, stirred for 1 hour, then quickly ^{heated to 200 °} C. and stirred at this temperature for 6 hours.

When the reaction has ended, the mixture is ^{cooled to 110 °} C., 75 kg of acetic anhydride are added dropwise over the course of 20 minutes and ^{the mixture is stirred at 110 °} C. for 2 hours. It is then ^{cooled to 20 °} C., 200 l of methanol are added, the mixture is stirred for 1 hour and the product is isolated on a pressure filter. A pure, orange-yellow, strongly fluorescent dye is obtained in good yield, consisting of a mixture of isomers of the formulas

OCOCH.

030051/0039

Example 4

A mixture of 79.5 kg of 10-methoxybenzoxanthene-3,4-dicarboxylic acid anhydride, 37.5 kg of phenylacetic acid, 25 kg of potassium acetate and 200 kg of N-methylpyrrolidone is heated ^{to 180 ° C. in a stirred tank.} After a further stirring time of

1 hour at 180 ⁰ C is heated further to 200 ⁰ C and stirred for 8 hours at this temperature.

When the reaction has ended, 25.4 kg of 50% strength sulfuric acid are added ^{at 190-200 ° C. over the course of 25 minutes.} The reaction mixture is cooled to 120 ⁰ C, at 120-160 ⁰ C and about 65 to 95 mbar (50-70 Torr) acetic acid and water up to a head temperature of 160 ⁰ C at 80 mbar (60 Torr).

When the distillation is over, 121 kg of N-methylpyrrolidone are obtained and at 120 to 123 ° C within 25 minutes

2 7.5 kg of potassium carbonate were added. The reaction mixture is stirred for 30 minutes at 120 ⁰ C and then at 80 - 85 ⁰ C cooled. It will further 5.6 kg of potassium carbonate and methylated at 8O ⁰ C 60.5 kg of dimethyl sulfate within 1-2 hours. When the reaction has ended, stirring is continued for 2 hours at 80-85 ^° C., then the product is ^{precipitated at 65 °} C. with 161 kg of methanol, the mixture is ^{cooled to 5-10 °} C., stirred for 1 hour and the dye is isolated on a pressure filter. An orange-yellow, fluorescent dye consisting of a mixture of isomers of the formulas is obtained in good yield

^H 3 ^C0

and

OCH.

0300S1 / 0Ö39

Example 5

In a stirred vessel, a mixture of 400 kg o6-chloronaphthalene, 104.6 kg phenylacetic acid and 62.8 kg of potassium acetate is heated to 80 ⁰ C. 196 kg of benzothioxanthenic acid-3,4-dicarboxylic acid anhydride are then added and the mixture is ^{heated to 180 °} C. over the course of 2 hours. After stirring for 1 hour at 18O ⁰ C the reaction mixture to 200 - 210 ⁰ C heated and stirred for 8-10 hours at this temperature.

After the reaction has ended, as in Example 1, 3 kg of 50% strength sulfuric acid are added ^{at 190-200 ° C. over the course of 30 minutes.} The reaction mixture is ^{cooled to 120 °} C. and at 120-130 ^° C. and about 65 to 95 mbar (50 70 torr) acetic acid and water are ^{distilled off up to a top temperature of 130 °} C. at 80 mbar (60 torr).

Is the distillation ended, 300 kg 06-chloronaphthalene was added at 80 - 85 ⁰ C methylated 160 kg of dimethyl sulfate within 1-2 hours. The reaction is complete, is stirred for 2 hours at 80 to 85 ° C and then the product with 400 kg of methanol at 30 ⁰ C - like 40 ⁰ C and at 15 ° C isolated on a pressure filter. The bluish-red, pure, strongly fluorescent dye according to Example 1 is obtained in good yield.

Example '6

76 kg of benzothioxanthene-3,4-dicarboxylic acid anhydride, 37.5 kg of phenylacetic acid, 25 kg of potassium acetate and 200 kg of hexamethylphosphoric acid trisamide are heated ^{together to 180 ° C. in a stirred tank.} After stirring for 1 hour at 180 ⁰ C is further heated to 200 ⁰ C and stirred for 6 hours at this temperature.

030051/0039

When the reaction has ended, the mixture is cooled to 110.degree. 75 kg of acetic anhydride are then allowed to run in over the course of 20 minutes and the mixture is subsequently stirred at 110 ^° C. for 2 hours. It is then ^{cooled to 20 °} C., 200 l of methanol are added, the mixture is stirred for 1 hour and isolated on a pressure filter. The pure, bluish-red, fluorescent dye according to Example 2 is obtained in good yield.

030051/0039

Claims (4)

Patent claims: 1. Process for the preparation of isomer mixtures of Compounds of the general formula Ia and Ib R, · and Yes wherein X is an oxygen or sulfur atom, R is an optionally substituted alkyl radical, acyl radical or benzenesulfonyl radical, R ₁ and R _{2 are} hydrogen or halogen atoms, alkyl, phenyl, acyl, acyloxy, carbalkoxy, alkoxy, nitro, alkylthio - Or alkylsulfonyl groups or together a fused benzene ring, R ₃ and R, hydrogen or halogen atoms, phenyl groups, alkyl, alkoxy, carbalkoxy groups with 1 to 4 carbon atoms or nitrile groups, R ₅ and R _{g with} hydrogen atoms or optionally substituted alkoxy groups with 1 to 4 carbon atoms mean
by heating compounds of formula II or III or II III 030051/0039 HOE "79 / F where X, R-., R., R ₁ - and R _{ß have} the meanings given above and R_ denotes a hydrogen atom or an alkyl group,
with compounds of the formula IV and / or V IV where R ₁ , R ~ and R_ have the meanings given above and R _{R is} a hydrogen atom or a hydroxyl group, in the presence of alkali to temperatures between about 150 and about 260 ⁰ C and then alkylating or acylating the mixture of isomers of the formulas VIa and VIb and wherein X, R .., R ₃ , R ₃ R., R ₅ and R _{g have} the meanings given above, characterized in that the reaction is carried out in a strongly polar organic solvent without isolation of the Isomer mixture of the formulas VIa and VIb carries out. 2. The method according to claim 1, characterized in that 030051/0039 HOE 79 / F 13 ^ - ys - one strongly polar solvent is N-methylpyrrolidone begins. 3. The method according to claim 1 and 2, characterized in that the condensation at 200 - 21O ⁰ C is performed. 4. The method according to claim 1 to 3, characterized in that that the end product from the reaction solution with a lower alkanol is precipitated. 030051/0039